Reaction products of polyvinylsulfonates with c-amino-pyridines



REACTION PRODUCTS F POLYVINYLSULFO- NATES WITH C-AMINO-PYRIDINES DelbertD. Reynolds and William 0. Kenyon, Rochester,

N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., acorporation at New Jersey No Drawing. Application September 29, 1951,

Serial No. 249,012

16 Claims. (Cl. 260-793) This invention relates to polyvinyl resins, andmore particularly to polyvinyl resins containing pyridylamine nuclei,which are suitable as mordants in photographic materials.

It is known that alkyl and aryl polyvinyl sulfonates can be reacted withprimary and secondary amines to give amino derivatives which possessaffinity for acids and thereby can: function in many instances asmordants. However, the usefulness of such amino derivatives, which areessentially N-substituted polyvinylamines, is quite limited. Forexample, attempts to use them as mordants in photographic layers havenot proven entirely successful, the acid dye compounds tending todiffuse somewhat from desired fixed positions so that poor definitionresults.

While tertiary amines will also react with alkyl and aryl polyvinylsulfonates as set forth in our copending application Serial No. 87,577,filed April 14, 1949 (now U. S. Patent No. 2,571,761, dated October 16,1951), the resulting products consisting essentially of poly-N-vinylpyridine quaternary salt units, and tetrahydropyran units in thepolymer chain, are water-soluble and considerably less suitable asmordants for fixing acid dyes in photographic layers, but having utilityas dispersing agents for silver halides;

We have now found that superior mordants for acid dyes in photographiclayers are obtained by reacting alkyl and aryl polyvinyl sulfonates,prepared as described in our patents U. S. 2,531,468 and U. S.2,531,469, both dated November 28, 1950, under controlled conditions;with C-aminopyridines or alkyl group substituted C- aminopyridines. Theresinous products thus obtained are of a more complex nature than thoseobtainable when only unsubstituted pyridine or picolines, that is,containing no free amino group substituent are employed. The completestructure of the new N.-substituted polyvinylamines of our inventionisnot known, but evidence indicates that they consist of pyridylamineunits and quaternized vinyl sulfonate: unitsalong with some vinylalcohol and cyclic ether units. The sulfur which is always present. inour new products is present principally in the-form of the quaternizedsalt units. Two principal reactions have beenfound' to take place:

wherein m represents zero, 1 or 2, R represents an alkyl, aralkyl oraryl group (e. g. methyl, ethyl, propyl, butyl, amyl, benzyl, phenyl,etc. groups) and R1 represents an atom of hydrogen or an alkyl groupcontaining from 1 to 5 carbon atoms. The nitrogenous portion of thepolymer molecule is represented entirely by the recurring product unitsrepresented instructural forms in the above equations.

The cyclic ether units present in our new poly- United States Patent 02,701,243 Patented Feb. 1, 1955 mers in substantial amount can berepresented by the recurring stuctural unit:

and form part of the linear polymer chain. The presence of the abovetype of cyclic ether units and the vinyl alcohol units do not materiallyinfluence the characteristic properties deriving directly from thepresence of the vinyl pyridylamine units and alkyl substituted vinylpyridylamine units and quaternary salt units illustrated in Equations 1and 2.

The above described new class of resins are linear type polymers whichare soluble in organic solvents such as methanol, but insoluble inwater. However, when R1 is small as in hydrogen or methyl, they aresoluble in dilute aqueous acid solutions such as 0.5,to 5% aqueoussolutions of mineral and organic acids including hydrochloric acid,hydrobromic acid, phosphoric acid, sulfuric acid, acetic acid,chloracetic acid, etc. However, higher .concentrations of the acids canbe used to dissolve the resins, if desired. The new polymers readilyform substantially water-insoluble salts with water-soluble acid dyes.They are also compatible with colloidal materials such as gelatin. Theseproperties, together with the relatively large molecular dimensions,make the new polymers outstanding mordants for fixing soluble acid dyessuchas those employed in photographic layers. They are particularlyvaluable as mordants in preventing the diflusion of the dyes whenincorporated in light filter layers, in backing layers designed toprevent back reflection from the film support and in imbibitionprintingblanks, where the process involves dye transfer from a tanned gelatinrelief to the gelatin-dye-mordant composition coated cellulose ester,synthetic resin, paper or similar support. Other colloids such as.polyvinyl alcohol can be employed in place of. gelatin. Also, othermaterials can be added to the composition of gelatin-mordant-dye such assilver halide dispersed therein so that there is obtained a materialwhich functions both as a light-sensitive photographic element andasanimbibition blank.

It is, accordingly, an objectof the invention to provide a new class ofpolyvinyl resins containing aminopyridine nucleiw as sidechains. Anotherobjectis to provide a photographic element having one or more layerscontaining the new resins of the invention. Another object is to providea light filter layer whereinis incorporated one or more resins oftheinvention. Another object is.to.provide a backing layer containing aresin of the invention for backing light-sensitive films to prevent backreflection of lightv from. the support. Another object is to provide animbibition type printing blank containing a resin of the invention.Another object is to provide a light-sensitive photographic layercontaining a resin of the invention. Another object is to provideprocesses for preparing the new resins and the photographic rraterials.Other objects. will become apparent hereina ter.

In accordance with the invention, we prepare our new polyvinyl resinscontaining aminopyridine nuclei as sidechains by starting with polymersof alkyl and aryl vinyl sulfonates, which compounds are in fact binarycopolymers consisting predominantly of vinyl sulfonate units combinedwith some residual vinyl alcohol units, that is, containing therecurring structural units:

wherein R has the previously defined meaning, and reacting the sulfonatewith a C-aminopyridine or a C- aminopyridine having one or two alkylgroup substituents on nuclear carbon atoms and, on completion of thereaction, precipitating the reaction mixture into a nonsolvent liquidsuch as water. However, other appropriate and common means forseparation of resinousproducts fromreaction mixtures can alsobeemployed. The product obtained is then further purified byredissolvingin methanol, adjusting the pH to" approximately 9 with analkaline'material (e. g. aqueous or alcoholic sodium or potassiumhydroxide) and reprecipita'ting into water and drying. The proportion ofreactants can be varied quite widely, but the C-aminopyridine or C-alkylsubstituted aminopyridine is generally employed equal to or in excess ofstoichiometric proportions, from 1 to mol of the particularaminopyridine to each mol of the particular polyvinyl sulfonate. Thetemperature of the reaction can vary from 60 C. to the boiling point ofthe reaction mixture, but preferably from 60 to 100 C. for the bestresults. Advantageously, the reaction can be carried out in an inertdiluent or mixtures of inert diluents such as in chloroform, acetone,etc. The aqueous or alcoholic alkali hydroxide solution functions toneutralize the sulfonate groups liberated in the reaction and,accordingly, need be present only to a slight excess although largeramounts are not harmful. The proportion of effective units in our newclass of polymers range from to 60% by weight of quaternary salt unitsand from 6% to 24% by weight of vinyl pyridylamine or vinyl C-alkylsubstituted pyridylamine units, the remainder of the polymer beingcyclic ether units and some residual vinyl alcohol units.

Suitable aminopyridines and C-alkyl substituted aminopyridines includeZ-aminopyridine, 4-aminopyridine, the aminopicolines such as2-amino-31nethylpyridine, 2- amino-4-methylpyridine,2-amino-S-methylpyridine, 2- arnino-6-methylpyridine and corresponding4-amino methyl derivatives which react in this reaction in exactly thesame way, Z-amino-6-ethylpyridine, 2-amino-6-butylpyridine,2-amino-6-amylpyridine, etc., the various aminolutidines such as, forexample, 4-amino-2,6-dimethyl o pyridine and the various aminocollidinessuch as, for example, 2-amino-3-ethyl-4-methylpyridine, etc.

The following examples will serve to illustrate further our new class ofpolymers and the manner of their preparation.

EXAMPLE 1 1200 g. of polyvinyl benzene sulfonate containing 83.4% byweight of vinyl benzene sulfonate units, and 16.6% by weight of vinylalcohol units, were stirred with 5800 g. of 2-amino pyridine on a steambath for 21 hours. The reaction mixture was cooled and poured intowater. The polymer which separated was redissolved in methanol andprecipitated by pouring the solution into dilute aqueous sodiumhydroxide solution. The resinous precipitate was then leached in water,dissolved in methanol, the solution filtered and precipitated into etherand the precipitate dried. It was soluble in dilute 1% aqueoushydrochloric acid. Analysis of the product gave by weight 5.0% sulfurand 9.2% nitrogen, corresponding to a calculated content therein ofapproximately 20.6% by weight of vinyl N-(2-pyridyl) amine units andapproximately 43.4% by weight of N-vinyl-2-amino pyridinium benzenesulfonate units, the said units having the structures and EXAMPLE 2 1900g. of polyvinyl benzenesulfonate, containing 84% by weight of vinylbenzene sulfonate units and approxi-' mately 16% by weight of vinylalcohol units and only a trace of chlorine, were dissolved in 6 litersof chloroform containing 2700 g. of 2-aminopyridine. The reaction washeated on a steam bath (60 to 100 C.) for 20 hours, the chloroform beingallowed to distill out during this time. An equal volume of methanol wasadded and the polymer was separated by precipitation of the solution inwater. It was redissolved in methanol, the pH of the solution adjustedto 10 with alcoholic sodium hydroxide and again precipitated in water.Further purification was efiected by trituration of the resin in waterat 6065 C. Analysis showed it to contain vinyl N-(2- pyridyl)amine andquaternary salt units in approximately the same proportion as the resinof Example 1. The resin, obtained as above, was dissolved in 250 cc. ofglacial acetic acid plus 1 liter of water to give 3047 g. of solutionwith a solid content of 35% (1080 g. solid) and having a pH of 4.2. Thissolution was incorporated into various light-sensitive gelatino-silverhalide emulsions and proved to be an unusually effective mordant.

EXAMPLE 3 g. of polyvinyl benzene sulfonate, containing 83.4% by weightof vinyl benzene sulfonate units and 16.6% by weight of vinyl alcoholunits, were dissolved in a mixture of 300 cc. of chloroform and g. of 2-amino-B-methylpyridine. The reaction mixture was heated on a steam bath(60-100 C.) for a period of 20 hours, during which time the chloroformwas allowed to distill out. Residual chloroform was removed undervacuum. The reaction product was dissolved in cc. o'i methanol and thepolymer was separated by precipitation of the solution in water. It wasthen redissolved in methanol, the pH adjusted to 9 by alcoholicpotassium hydroxide and the polymer again isolated by precipitating inwater. The product was then dissolved in 100 cc. of methanol, thesolution filtered and precipitated in a 2:1 mixture of ether andethanol. The polymer was light yellow and became granular on drying. Itwas soluble in 1% aqueous hydrochloric acid. Analysis of this productgave by weight 6.0% of sulfur and 7.4% of nitrogen, corresponding to acalculated content therein of approximately 10% by weight of vinylN-(2-(3-methyl)pyridyl) amine units and approximately 55% by weight ofN- vinyl-2-amino-3-methyl pyridinium benzene sulfonate units, the saidunits having the structures CHI and

EXAMPLE 4 100 g. of polyvinyl benzene sulfonate containing 83.4% byweight of vinyl benzene sulfonate units and 16.6% by weight of vinylalcohol units were stirred with 500 g. of 2-amino-4-methyl pyridine on asteam bath for a period of 20 hours. The reaction mixture was cooled andthe polymeric product separated by precipitation of the mixture intowater. The polymer obtained was redissolved in methanol and sufficient10% aqueous sodium hydroxide solution added to give a pink color to thesolution with phenolphthalein indicator. The solution was then filteredand poured into a larger volume of water. The polymer which separatedwas washed with water and dried. It was soluble in dilute mineral acidsand on analysis gave by weight 5.9% of sulfur and 9.1% of nitrogen,corresponding to a calculated content therein of approximately 19% byweight of vinyl N-(2-(4-methyl)- pyridyl)arnine units and approximately54% by weight of N-vinyl-2-amino-4-methylpyridinium benzene sulfonateunits, the said units having the structures color -'to 'phenol'phthaleinindicator.

: P'Q y j water. :It was redissolved in methanol, the pHad usted enemasand EXAMPLE 5 100 g. of polyvinyl benzene sulfonate containing 83.4%

weight "or vinyl alcohol units were stirred with 500 g. :or '2amino-5-metl1yl pyridine-and heated at90"-to 100 'C. "ona'stearn bathfor hours. The reaction mixture was cooled and the polymeric pro'ductprecipitated in water. 'Thefpol-ymer was redissolved in methanol andsufficient 10 aqueou-s sodium hydroxide added to give a pink Theresulting solution was pouredinto ether. The polymer which separated waswashed and dried. It was soluble'in 1% aqueous "hydroehlor'icacid-and onanalysis'was shown to contain by weight 5.9% "of sulfur and 8.9% ofnitrogen, corresponding to a calculated content thereinof approximately18% by weight of vinyl N-(Z-(5-methyl)pyridyl)amine unitsan'dapproximately 54% by weight of N-vinyl-Z- amino-5 methylpyridiniumbenzene sulfonate units, the said units. having the structures -.-asteam.bath;(60100 C.) I for a period ofu-2.0 hours, .:during which1timethe chloroform was allowed to distill out. Residual chloroform wasremoved under vacuum.

The reaction product was dissolved in methanol and'the separated byiprecipitation of the solution in to-9 by alcoholic potassium hydroxideand the polymer .againisolated by precipitating in water. It was then re.dissolved in methanol, the solution filtered andpreciprtated in a 2:1mixture of etherand ethanol. The poly- ,mer-was lightyellow and becamegranularon drying. It

was soluble in 1% aqueous hydrochloric acid. 'Analysis of this productgave by weight 5.9% of sulfur and 8.3% of nitrogen, corresponding t'oacalculate'd content therein of. approximately 451% by weight -of vinylN-.(-.2-(6- methyl)pyridyl)amine units and approximately 54% by weight=of N-vinyl-Z-amino-6-methylpyridinium benzene sulfonate units, the saidunits having the structures by precipitation into water.

:EXAMPLE 7 300 g. of sodium amide were ground in a mortar with 450 g. ofZ-n-amylpyridine. The mixture was heated'at about 125 C. and stirredforL'S hours. The cooled mixture was hydrolyzed with ice water. Anexcess of sodium hydroxide was added and the top .layer separated. Thebottom layer was extraoted with benzene and the benzene extract combinedwith the original top layer. After drying over anhydrous calciumchloride, the benzene was removed by distillation and the reactionproduct distilled under vacuum without fractionation. The crude materialwas then purified by .frac'tion'al Ldistillation. There was obtained afraction of 200g. boiling at 96 C./0.5 mm. Analysis of "this fractiongave by weight 73.4% "carbon,

"9.5% hydrogen and 16.6% nitrogen ('cornparedwith calculated theo'ry of73.1% C, 9.7% Hand 17.0% 'N) indicating thereby thatpracticallypure'2-'amino-'6-'a'mylpyridine had been obtained.

7 8 g. of polyvinyl benzene sulfonate-were dissolved in 50carat-chloroform containing 25 g. of "2-amino-6-amylpyridine (preparedas above described). The reaction mixture was heated for '16 :hours on asteam bath (6'0-'l 00 'C..) and the chloroform allowed to distill. 'The'polymer Was'precipitated in ether and then'redissolved inme'thanol. The.pH of the'solution was'adjusted-to'9'and the polymer was separated byprecipitation in water. It was again dissolved inmethanol and:precipitated'in water.

'The light brow'n'polymer obtained was insoluble in dilute .acetic'acid.Analysis of'the polymerg'ave 'by weight 5.9% of'sulfur and "6.9% ofnitrogen, corresponding "to a cal- "cula'te'd content j therein :ofapproximately 8% by weight of vinyl 'N-( 2-:'( G-amy Dpyridyl) :amine'unitsand approxi- Bysubstitutingzthe Z-mamylpyridinein theiaboveexamplewith various other. 2*n-alkyl pyridines, there can be. .pre- ,paredgenerally similarpolyrners characterized lay-contain- .ing thecorresponding ivinylN-2-amino-alleyl pyridine units.

EXAMPLE? 1'7 g. of polyvinyl benzene sulfonate, containing :83:4I% byWeight of vinyl benzene sulfonate units and 16.6% by weight of vinylalcohol units, and '25g. of2-amino-4,6-

"dimethyl pyridine 'were dissolved 'tog'ether ii'n I =cc. of

chlorofo'rm. This l=reaction mixture was ihe'a'te'd for hourson=asteamibath, 'during'which' tim'e the-chloroform was allowed todistill. The resinous productwas i'solated It was then dissolved inmethanol. The solution was filtered, the pH adjusted to 9.5 withalcoholicf'potassium hydroxide and againpoured into water. The driedpolymer was again dissolved in methanol, precipitated a 1:1 mixtureofal'cjol'rol ether and hardened by leaching in ether. The resultinglight yellow brittle polymer which was Water-insoluble but sol- .uble in'dilutefaqueous acids, contained7.'5.'% 'byweight of nitrogen'and 5.5%by weight'of'sulfur, corresponding toa calculated content therein ofapproximately 13 by 7 total of 20 pounds.

but prior to the diacetyl solution.

4,6-dimethyl pyridinium benzene sulfonate units, the said units havingthe structures and EXAMPLE 9 This example illustrates the effectivenessof the new polyvinyl resins of the invention as mordants in photographicfilter and backing layers to prevent diffusion of the dye from suchlayers into overcoating layers.

(a) Gelatin-dye layer To 4540 g. of an aqueous gelatin solutioncontaining 10% by weight of dry gelatin, there was added enoughdistilled water to bring the weight to 15 pounds and the mixture heatedto 40 C. Next, there was added with stirring 120 cc. of an aqueous 8%saponin solution, then there was added with stirring a solutioncontaining 34 g. of his [1-(p-sulfophenyl)-3-methyl-5-pyrazolone (4)]methine oxonol dissolved in 1000 cc. of distilled water and adjusted toa pH of 5 .0 with dilute sodium hydroxide, and then there was added withstirring 120 cc. of an aqueous l.7% diacetyl solution. The pH of thewhole mixture was adjusted to 5.0 with dilute sodium hydroxide andsufficient distilled water mixed therewith to make a The. completedmixture was then coated on a clear safety film support at the rate of0.04 pound of the mixture per square foot of film support. After curing,the coated side of the film support was overcoated with a bromoiodideemulsion of the type described by Trivelli and Smith, Phot. I. 79330-338 (1939), containing one mole of silver halide and 308 g. ofgelatin in a total weight of 9.5 pounds, to which there had been added120 cc. of aqueous 8% saponin solution, 120 cc. of aqueous 1.7% diacetylsolution and enough distilled water to bring the total weight to 14pounds. The rate of coating was 0.002 mol of silver halide per squarefoot of film area.

(b) Gelatin-dye-mora'ant layer Another sheet of clear safety filmsupport was coated and overcoated as described in above (a) except thatthe first coating adjacent to the support contained, in addition to theother ingredients of (a), 64 g. of a polyvinyl resin containingapproximately 44% by weight of N-vinyl-Z- aminopyridinium benzenesulfonate units and approximately 14% by weight of vinyl N-(Z-pyridyl)amine units.

In this case, the resin was added subsequent to the dye The resin wasdissolved in an aqueous solution containing 120 cc. of glacial aceticacid in a total volume of 1600 cc., the solution being first adjusted toa pH of 4.0 with dilute sodium hydroxide.

v (c) Photographic testing of products (a) and (b) The photographictesting of above sensitized products gave the following results, wherespeeds are expressed as /i where i is inertia in meter candle seconds ofsunlight quality.

Product Speed Gamma difiusion of the dye into the emulsion coat, whichaccordingly had higher speed and contrast.

EXAMPLE 10 (a) Gelatin-dye layer This product is the same as Example 9(a) except that 7.2 g. of the dye 4-[3-ethyl-2 (3)-benzoxazolylidene(ethylidene)] -3-methyl-1-p-sulfophenyl-5-pyrazolone in 1000 cc. ofdistilled water, adjusted to a pH of 5.0 with dilute sodium hydroxide,was used in the first coating instead of 34 g. of the dye bis[1-(p-sulfophenyl)-3-methyl-5-pyrazolone (4)] methine oxonol.

(b) Gelatin-dye-mordant layer This product is the same as above (a)except the first coating adjacent to the support contained, in additionto the other ingredients of (a), 14.4 g. of the same polyvinyl resin aswas used in Example 9 (b). In this case, the order of addition was alsothe same, except that the resin was dissolved first in 30 cc. ofconcentrated acetic acid and then diluted to 300 cc. with distilledwater, then adjusted to pH of 4.0 with dilute sodium hydroxide andfinally diluted to a total volume of 350 cc., in which form it wasincorporated into the gelatin-dye mixture.

The overcoatings of above products (a) and (b) were carried out with thesame emulsions and procedure as described in Example 9.

(c) Photographic testing of products (a) and (b) Product Speed GammaHere again the lower speed and contrast of the product (a), comparedwith the product (b), shows the effect of diffusion of another yellowdye from the first coat into the gelatino-silver halide overcoat. Inproduct (b), mordanting of the dye by the polyvinyl resin contained inthe first coat is again shown to reduce greatly the diffusion of the dyeinto the emulsion overcoating, which latter accordingly had a higherspeed and contrast.

EXAMPLE 11 This example illustrates the advantageous results obtained bythe incorporation of the new polyvinyl resins of the invention asmordants to prevent dye bleeding in dye transfer processes employingpro-sensitized (silver halide) dye blanks.

(a) Emulsion without mordant A bromoiodide emulsion of the typedescribed by Trivelli and Smith (see reference Example 9) having aweight of 9.5 pounds per mol of silver halide and containing 308 g. ofgelatin was prepared. To this emulsion there was added 44 cc. of 50%glycerine solution plus 40 cc. of approximately 6% saponin solution, andafter adjustment of the pH to 5.0 with sulfuric acid, there were added20 cc. of 10% formaldehyde solution and sufiicient distilled water tobring the total weight of the mixture to 11 pounds. This mixture wascoated at the rate of 0.0038 mol of silver halide per square foot on aclear safety film support.

(b) Emulsion with mordant Into a bromoiodide emulsion similar to that ofabove (a), there were incorporated 40 cc. of 50% glycerine solution, 40cc. of 6% saponin solution and 850 cc. of 4% solution of the same resinas was used in Example 9(b) in 10% acetic acid adjusted to a pH of 5.0.The pH of the entire mixture was then adjusted to a pH of 5.0. Then 15cc. of 10% formaldehyde solution and enough distilled water were addedto bring the total weight of the mixture to 12.7 pounds per mol ofsilver. This mixture was also spread on a clear safety film support atthe rate of 0.0038 mol of silver halide per square foot of film support.

:.-harde,ner.

('0) lnibibiti on-testing I :XI he products of 2 above a).;and :(h) weresgiyen suitable pre-conditioning to ensure adequate hardening,

and-were-athen" processed and tested .aszdye rinibibition vlblanlts.Product (b) containing thewnew :resinvas =a .nnordantshowed considerablybetter :definition and sharptnesstof .image than :product (a) which:containedrnone ..cent. solution in-dilutecaqueous acetic-acid of:ajpolyvinyl .resin containing approximately-44 per cent by weight of.N-vinyl-Z-aminopyridinium benzene isulfonate units and approximately14:,per .cent by weight :of N-(2 pyridyl) amine units. The total weightof the mixture was adjusted to :15 pounds \by the addition of distilledwater. The pH wasradjusted to.5.0, followed bythe addition of 30 cc. ofper 'cent formalin inwater solution as a rcine support.

(b) Blank without mordant /.A mixture was made similar to above (a), butwithout the polyvinyl resin, and similarly-coated.

'The above coatings were in each case made :at'the rate of 0.0025 poundof gelatin per square foot. These coatings were conditionedbyincubatinguntil hardened, and

-.-.were;then tested in the following manner:

'Prior to the yellow dye transfer step, the :blanks-,prepared as abovewere first soaked for about one minute in a one per cent solution ofsodium sulfosalicylate, pH 4.9, at 75 F. In the steps of transfers ofthe cyan and magenta dyes, the blanks were soaked for about one minutein tap water at 75 F. Suitable gelatin relief matrices were dyed withthe proper dyes for two minutes, rinsed seconds at 80 F., and laminatedin contact with blanks (a) and (b) for two minutes at 110 F. Resolvingpower test charts showed very much better definition got the blanks (a)containing the polyvinyl resin mor ant.

Although the invention has been illustrated with only a limited numberof the new resinous polymers of the invention, it will be understoodthat similarly good mordanting properties are possessed by all the newresinous polymers of the invention, including those which contain 6%,15%, 18%, 21% or 24% by weight of vinyl pyridylamine or C-alkylsubstituted vinyl pyridylamine units and 40%, 45%, 50% or 60% by weightof quaternary salt units. Also, various other sheet materials can beemployed as supports for the described photographic materials containingthe new resinous polymers of the invention. For example, celluloseesters such as the nitrate, acetate, acetate-propionate,acetate-butyrate, etc.,.

and, snythetic resins such as polyvinyl acetal, polyvinyl butal, etc.,can be employed, and in the case of the gel coated dye transfer blanks,opaque or semi-opaque materials such as pigmented cellulose esters,paper, etc., can also be used.

What we claim is:

1. A process for preparing a polyvinyl resin containing from 6% to 24%by weight of a vinyl sulfonate having the general formula:

wherein m represents a positive integer of from 1 to 3 and R1 representsa member selected from the group consisting of an atom of hydrogen andan alkyl group containing from 1 to 5 carbon atoms, and from 40% Themixture was coated on a clear safety nium benzene sulfonate units, whichcomprises reactinga 1'10: f'6 0% by' as hm quaternary "saltihaxiingiztheg'gen- I eral -formula:

wherein m and R1 "have l the; above "definitions =and;'-R represents amember: selected from the .group "COfiSlStli'lg of an alkyl groupcontaining fr'om l'to 5carbon -atom'js,

wherein "m and R1 '"have the above-.dfinition's, at a temperature offrom 60 C.- to the refluxing temperature 'of'ithe .reaction mixture atatmospheric pressure, "in the ratio 'o'ffro'm lto 15 mol ofthe'saidaminopyridine .to .reach mol df the .saidfpolyvinyl s ulfonate, "andseparating "the polyvinyl resinfprotluct which forms 'from'the reactionmixturer "2. 'Aprocess' ofpreparing"apolyvinyl resin containing from 6%to.24% by weight of vinyl .N-.( .-pyridyl) amine units and from 40%t0"'60% "O'f "N-Vinyl'-2'-'aminopyridiwherein R represents a memberselected from the group consisting of an alkyl group containing from 1to 5 carbon atoms, a phenyl group and a benzyl group, with2-aminopyridine, at a temperature of from 60 to C., in the ratio of from1 to 15 mol of the 2-amino pyridine to each mol of the polyvinylsulfonate, and separating the polyvinyl resin product which forms fromthe reaction mixture.

3. A process for preparing a polyvinyl resin containing of from 6% to24% by weight of vinyl N-[2-(3-methyl) pyridyl] amine units and from 40%to 60% by weight of N-vinyl-2-amino-3-methyl pyridinium benzenesulfonate units, which comprises reacting a polymer of a. vinylsulfonate having the general formula:

wherein R represents a member selected from the group consisting of analkyl group containing from 1 to 5 carbon atoms, a phenyl group and abenzyl group, with 2-amino-3-methylpyridine, at a temperature of from 60to 100 C., in the ratio of from 1 to 15 mols of the2-amino-3-methylpyridine to each mol of the polyvinyl sulfonate, andseparating the polyvinyl resin product which forms from the reactionmixture.

4. A process for preparing a polyvinyl resin containing from 6% to 24%by weight of vinyl N-[2-(4-methyl pyridyl] amine units and from 40% to60% by weight of N-vinyl-Z-amino-4-methyl-pyridinium benzene sulfonateunits, which comprises reacting a polymer of a vinyl sulfonate havingthe general formula wherein R represents a member selected from thegroup consisting of an alkyl group containing from 1 to 5 carbon atoms,a phenyl group and a benzyl group with Z-amino-4-methylpyridine, at atemperature of from 60 to 100 C., in the ratio of from 1 to 15 mols ofthe 2-amino-4-methylpyridine to each mol of the polyvinyl sulfonate, andseparating the polyvinyl resin product which forms from the reactionmixture.

5. A process for preparing a polyvinyl resin containing from 6% to 24%by weight of vinyl N-[2-(6-amyl) pyridyl] amine units and from 40% to60% by weight of N-vinyl-2-amino-6-amy1 pyridinium benzene sulfonateunits, which comprises reacting a polymer of a vinyl sulfonate havingthe general formula CH2=CH O-SO2-R wherein R represents a memberselected from the group consisting of an alkyl group containing from 1to 5 carbon atoms, a phenyl group and a benzyl group, with wherein Rrepresents a member selected from the group consisting of an alkyl groupcontaining from 1 to 5 carbon atoms, a phenyl group and a benzyl group,with 2-amino-4,6-dimethylpyridine, at a temperature of from 60 to 100C.,in the ratio of from 1 to 15 mols of the 2-amino-4,-dirnethylpyridine toeach mol of the polyvinyl sulfonate, and separating the polyvinyl resinproduct which forms from the reaction mixture.

7. The product prepared according to the process of claim 1.

8. The product prepared according to the process of claim 2.

9. The product prepared according to the process of claim 3.

10. The product prepared according to the process of claim 4.

11. The product prepared according to the process of claim 5.

1 12. 'he product prepared according to the process of c aim 13. Theproduct prepared according to the process'of claim 2, wherein the vinylN-(2-pyridyl) amine units constitute approximately 20.6% by Weight andthe N-vinyl- 2-amino pyridinium benzene sulfonate units constituteapproximately 43.4% by weight of the product.

14. The product prepared according to claim 3, wherein the vinylN-[2-(3-methyl) pyridyl] amine units constitute approximately 10% byweight and the N-viny1-2- amino-3-methyl-pyridinium benzene sulfonateunits constitute approximately by weight of the product.

15. The product prepared according to claim 4, wherein the vinylN-[2-(4-methyl) pyridyl] amine units constitute approximately 19% byweight and the N-vinyl-2- amino-4-methyl-pyridinium benzene sulfonateunits constitute approximately 54% by weight of the product.

16. The product prepared according to claim 5, wherein the vinylN-[2-(6-amyl) pyridyl] amine units constiute approximately 8% by weightand the N-vinyl-2-amino- G-amylpyridinium benzene sulfonate unitsconstitute approximately 54% by weight of the product.

References Cited in the file of this patent UNITED STATES PATENTS OTHERREFERENCES Reynolds et al., I. Am. Chem. Soc. 72, 1587-1590 (April1950).

1. A PROCESS FOR PREPARING A POLYVINYL RESIN CONTAINING FROM 6% TO 24%BY WEIGHT OF A VINLY SULFONATE HAVING THE GENERAL FORMULA: